Methods for fabrication and highway marking usage of agglomerated retroreflective beads

ABSTRACT

A retroreflective device securable to a highway by bonding thereto preferably with a viscous strip applied to the highway prior to solidifying cure of the strip includes a generally globular glass central member, a desirably pigmented adhesive layer over the central member and a plurality of peripheral globular glass members connected to the central member by the pigmented adhesive layer. A method for fabricating the retroreflective device is also disclosed.

CROSS-REFERENCE TO RELATED PATENT APPLICATIONS

This patent application is a continuation-in-part of pending U.S. patentapplication Ser. No. 13/590,729, filed 21 Aug. 2012 entitled “Methodsfor Fabrication and Highway Marking Usage of AgglomeratedRetroreflective Beads” which in turn is a division of U.S. patentapplication Ser. No. 11/789,421, now U.S. Pat. No. 8,292,539, granted 23Oct. 2012, entitled “Agglomerated Retroreflective Beads for HighwayMarking and Methods for Fabrication and Use Thereof.”

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates generally to highway striping and markingmaterials and specifically to retroreflective beads used in highwaystriping and marking materials to enhance visibility of the highway,where striped and marked, especially after sundown.

2. Description of Prior Art

Pavement markings such as paints, tapes, and individually mountedarticles to guide and direct motorists traveling along a roadway areknown. During daylight the markings may be sufficiently illuminated byambient light to effectively signal and guide motorists. At night,especially when the primary source of illumination is the vehicle'sheadlights, the markings may be insufficient to guide adequatelymotorists because light from vehicle headlights hits the pavement andpavement markings at a very low angle of incidence, with the result thatthe light largely reflects away from the vehicle.

Retroreflection is the mechanism whereby light incident on a surface isreflected in a way that much of the incident light is directed backtowards the light source. The most common retroreflective pavementmarkings, such as lane lines on roadways, are made by droppingtransparent glass or ceramic optical elements onto a freshly paintedline to which the optical elements adhere and desirably become partiallyembedded therein. Each transparent optical element preferably acts as aspherical lens. Incident light desirably passes through the opticalelements to the pavement marking paint or sheet, striking any pigmentparticles embedded therein. The pigment particles scatter the light. Thescattered light includes a portion that is directed back into theoptical element, which then redirects that portion of light back towardsthe light source.

In addition to providing desired optical effects, pavement markings mustwithstand road traffic, and adverse weather conditions, and are subjectto cost constraints in the course of manufacture and installation.

Vertically oriented or upwardly disposed surfaces provide goodorientation for retroreflection. As a result, attempts have been made toincorporate vertical surfaces in pavement markings, such as by providingprotrusions in the marking surface. Vertical surfaces may advantageouslyprevent build-up of water over the retroreflective surface during rainyweather, which water would otherwise interfere with retroreflection.

Sometimes raised pavement markers are placed at intervals along apavement marking line as disclosed in U.S. Pat. Nos. 3,292,507 and4,875,798. These markers are relatively large, generally being severalcentimeters in width, and five to twenty millimeters in height.Typically, such markers require assembly of different components, someof which were previously individually molded or cast. Therefore, suchmarkers are relatively expensive to manufacture. The size of the markersmakes them subject to substantial impact forces from passing vehicles.As a result, the markers must be well secured to the pavement,increasing installation costs and also removal costs when the markersmust be replaced. Moreover, because the markers are applied atintervals, the reflected light provided by the markers are in the formof discontinuous spots of light. A continuous bright line of reflectivelight is more desirable.

Embossed pavement marking tapes, as disclosed in U.S. Pat. Nos.4,069,281 and 5,417,515, represent an approach that has been takentowards providing better highway marking surfaces. Selective placementof transparent optical elements on the sides of embossed raisedprotrusions present in the tapes results in somewhat effective markingHowever, such tapes are relatively expensive compared to paintedmarkings and tend to pick up dirt that adheres to the tape even after ahard rain. As a result, tape usage is often limited lower traffic areassuch as unlighted intersections and railway crossings. These embossedtapes are constructed with polymeric materials which are susceptible towear.

Yet another approach to providing retroreflection is the compositeretroreflective element such as disclosed in U.S. Pat. Nos. 3,254,563and 4,983,458. These retroreflective elements essentially have a corewith optical elements embedded in the core surface. Some also containoptical elements dispersed throughout the core that become exposed withwear. The core may be irregular in shape or may be shaped as a sphere,tetrahedron, disc, square, tile, etc.

Some known retroreflective elements have centers formed of polymericcores or binders. A pigmented core or binder may serve as a diffusereflector, allowing spherical optical elements to be used on horizontaland vertical surfaces. Other constructions have transparent opticalelements including specular reflectors such as metallic silver. Themetallic surface directs light back towards the light source. In suchcases pigmented cores are not used. Geometry of the optics may make aspecular coated optical element less effective when embedded in pavementmarking paint on a horizontal surface, and more effective when embeddedin the vertical surfaces of a retroreflective support element.

Another retroreflective element construction, disclosed in U.S. Pat. No.3,252,376, uses silvered glass flakes as a specular reflector on thesurface of a spherical polymeric core; no spherical optical elements areused.

Still another known construction disclosed in U.S. Pat. Nos. 4,072,403;4,652,172 and 5,268,789 has a retroreflective element with a plasticglobule refracting incident light onto a layer of glass optical elementsattached to the bottom of the globule. The glass optical elements focuslight onto a specular coating or film located below the elements.Incident light is then reflected back along the original path towardsthe source.

Shaped polymeric retroreflective elements with pigmented cores and glassoptical elements embedded in the vertical surfaces are disclosed in U.S.Pat. No. 3,418,896. These retroreflective elements are formed byextruding pigmented polymer into rods of different cross-sectionalshapes. Glass optical elements are embedded into the surface of thepolymer before it hardens, then the rods are sliced to form theelements.

Polymeric retroreflective elements are undesirably susceptible to wear,especially in high traffic regions, and to degradation due toweathering.

In an attempt to overcome these limitations, retroreflective elementshave been constructed having a ceramic core surrounded by optical glasswith a metallic specular coating.

One such construction approach is a rock or glass sphere core asdisclosed in U.S. Pat. Nos. 3,043,196 and 3,175,935, covered by apolymeric binder with glass optical elements having a specular metalliccoating embedded in the polymeric coating.

Another construction disclosed in U.S. Pat. No. 3,556,637 includes aglass sphere and a layer of glass optical elements attached to thebottom of the glass sphere with a polymeric binder. A metallic filmbelow the glass optical elements acts as a specular reflector. However,these glass sphere-metallic film combinations do not provide thebrilliant white or yellow color for the reflective light that isdesirable in a high quality highway machine and is necessary to meet therequirements of many regulatory authorities. The glass sphere-metallicfilm approach tends to produce reflected light that is grey or silver,instead of white, or that is bronze or gold, instead of yellow. None ofthese are acceptable.

Other constructions include a composite lens element serving both as aretroreflective element and a skid-resistant particle as disclosed inEuropean patent 0,322,671. The skid-resistant particle, which acts as acore, may be either a corundum particle or glass sphere, and is coatedwith a pigmented polymeric binder acting as a diffuse reflector.

A ceramic element having glass optical elements embedded throughout aglass core and at the core surface is disclosed in U.S. Pat. No.3,171,827. A thin metallic film separates the optical elements and theglass core to provide an efficient specular retroreflective system.Alternatively, optical elements having a refractive index greater than2.0 are used. These high refractive index optical elements are assertedas being capable of reflecting light without the need for a reflectivebacking.

A ceramic retroreflective composite element having a transparent glasssphere with smaller glass optical elements embedded in the surface isdisclosed in U.S. Pat. Nos. 3,274,888 and 3,486,952. A thin metallicfilm separates the optical elements and the glass sphere to providespecular retroreflective system. The elements are formed by firstcoating the glass spheres with metallized optical elements using atemporary polymeric binder. The coated spheres are then tumbled withexcess optical elements in a rotary kiln. When temperature exceeds thesoftening temperature of the glass spheres, the optical elements embedthemselves into the surface of the spheres. Later the film is etchedaway from the exposed portions of the optical elements.

WO 97/28471 discloses a retroreflective element having an opacifiedceramic core and ceramic optical elements partially embedded in thecore. The diffuse reflecting ceramic core, in combination with thetransparent optical elements embedded in the surface, provides aretroreflective element asserted to be without the gray coloration andthe susceptibility to corrosion associated with metallic specularreflectors. Although such all-ceramic retroreflective elements areasserted to have improved resistance to wear and weathering,crush-resistance remains a problem, limiting life of the retroreflectiveelement.

Beads for highway marking are disclosed in U.S. Pat. Nos. 3,171,827 and3,274,888. '827 discloses a bead with a polymer core, while '888discloses beads consisting of all glass bonded to a glass core that isfabricated by melting these glass components together; there is nopolymer core nor is any adhesive used.

U.S. Pat. No. 4,983,458 discloses a bead similar to that disclosed in'827, but having a tetrahedron shape intended to increase adhesion tohighway marking tape. However, the '458 product does not function wellwith current reflective bead application equipment.

U.S. Pat. No. 5,456,546 discloses use of single glass beads in highwaymarking lines.

U.S. Pat. Nos. 5,774,265 and 5,917,652 disclose retroreflectiveelements. The elements are not white or yellow, which is desirable sincewhite and yellow are the colors used for highway striping and are, inmany instances, required by law. The retroreflective elements disclosedin '265 and '652 are expensive to manufacture.

U.S. Pat. No. 5,942,280 discloses a bead that is a variant of the beadsdisclosed in the '458 and '827 patents discussed above.

United States published applications 2005/0100709 and 2005/0158461disclose beads that are similar to the beads disclosed in the '458; '827and '546 patents discussed above, but the beads disclosed in these twopending patent applications are not all ceramic.

United States published application 2005/0001342 discloses anagglomeration of small beads without a core, manufactured by a slow,costly method.

SUMMARY OF THE INVENTION

In one of its aspects this invention provides an agglomerated bead forhighway marking having high retroreflectivity both when initiallyinstalled and over the bead lifetime, allowing vehicle drivers to seehighway marking lines at night. When installed the agglomerated beadsessentially match the color of the highway marking material in which theagglomerated beads reside.

In one of its several aspects this invention provides a retroreflectivedevice securable to a highway by bonding with a viscous strip applied tothe highway prior to solidifying cure of the strip, where the deviceincludes a generally globular glass central member, a pigmented adhesivelayer over the central member, and a plurality of peripheral globularglass members connected to the central member by the pigmented adhesivelayer. Preferably the central member is in the range of from about 14 toabout 20 mesh and the peripheral members are in the range of from about325 to about 400 mesh and further preferably cover the central member.Both the central member and the peripheral members are preferably ofgenerally spherical configuration; the pigmented adhesive layerpreferably includes both pigment and resin, with the pigmented layerpreferably being less than the diameter of the peripheral glass membersand where the pigmented layer preferably still further includes reagentsthat react adhesively during fabrication of the device to secure theperipheral members to the central member.

In yet another of its aspects this invention provides an agglomeratedbead, which after significant traffic passage thereover, wears at thetop of the agglomerate but maintains retroreflectivity withretroreflectivity largely being produced at the side of the agglomeratedbead, and with the exposed core of the agglomerated bead itself beingretroreflective.

The agglomerated beads may desirably be applied to a highway by trucksdropping exact amounts of the agglomerated beads on freshly appliedhighway marking line. The lines preferably utilize two componentchemistries such as epoxy, epoxy hybrids, polyurethanes and polyureas.When the agglomerated beads are applied, the line is flooded with theagglomerated beads. The line is ready for traffic in two to ten minutes,depending on the specific line chemistry used. Alternatively, theagglomerated beads may be mixed with small, bare retroreflective beads.

It is further within the purview of the invention to apply theagglomerated beads to a highway by trucks dropping exact amounts of theagglomerated beads on freshly applied thermoplastic or latex paint.

Formulation of the polymer coating and the adhesive layer affectsperformance. Blending steps in the manufacture of the agglomerated beadsare preferably performed in a fluidized mixer to distribute all layersuniformly and rapidly.

Control of timing for the addition, mixing and curing of each reagentsecures the desired properties of the final agglomerated bead product.

Agglomerated bead performance characteristics have been measured inseveral ways: color of the finished agglomerated bead; retroreflectivityof the bead by itself; retroreflectivity of the agglomerated bead in apainted highway marking line; color of the line after addition of theagglomerated beads as compared to color without agglomerated beads;retroreflectivity of the line after wear testing with traffic; and colorof the line with agglomerated beads after wear testing. ASTM E1710 forretroreflectivity and ASTM E1349 for color are the test methods used.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an artist's conception front elevation of an agglomeratedretroreflective generally spherical glass media for highway marking inaccordance with aspects of the invention.

FIG. 2 is an artist's conception sectional view, taken at lines andarrows 2-2 in FIG. 1, of the agglomerated retroreflective generallyspherical glass media shown in FIG. 1.

FIG. 3 is an artist's conception enlarged sectional view of a portion ofthe interior of an agglomerated retroreflective generally sphericalglass media for highway marking in accordance with aspects of theinvention, with the smaller exterior generally spherical glass membersillustrated largely embedded in an interior pigmented adhesive layerthat covers the larger interior generally spherical glass member, andwith the interior pigmented layer shown schematically as comprisingmultiple layers, to reflect in schematic form the process by which theagglomerated reflective generally spherical glass media of the inventionare fabricated.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION ANDBEST MODE FOR PRACTICE THEREOF

Referring to FIGS. 1, 2 and 3, in FIG. 1 a single agglomeratedretroreflective glass media in accordance with the invention isdesignated generally 10, with the exterior of agglomeratedretroreflective glass media 10 being essentially completely covered andexclusively defined by smaller generally spherical glass members,individual ones of which have been designated 14 in FIG. 1.

Referring to FIG. 2, the interior of agglomerated retroreflective glassmedia 10 is defined by a relatively larger generally spherical centralglass member designated 12. The smaller generally spherical glassmembers 14, defining the exterior of agglomerated retroreflective glassmedia 10 as illustrated in FIG. 1, are visible in FIG. 2. Securement ofsmaller generally spherical glass members 14 to relatively largergenerally spherical central glass member 12 is effectuated by pigmentedadhesive layer designated 16 in FIG. 2. Desirably, smaller generallyspherical glass members 14 are sufficiently embedded in pigmentedadhesive layer 16 that smaller generally spherical glass members 14rigidly and fixedly form part of agglomerated retroreflective glassmedia 10.

As further illustrated schematically in FIG. 2, the smaller generallyspherical glass members 14 are embedded in pigmented adhesive layer 16but preferably are separated by pigmented adhesive layer 16 from theexterior of relatively larger generally spherical central glass member12.

In FIG. 3, a broken portion of relatively larger generally sphericalcentral glass member 12 is depicted with several of the smallergenerally spherical central glass members 14 embedded in pigmentedadhesive layer 16, but separated by pigmented adhesive layer 16 from thesurface of relatively larger generally spherical central glass member12. In FIG. 3, pigmented adhesive layer 16 is depicted as consisting oftwo separate layers, a first inner schematic layer contacting theexterior of central member 12 and designated generally 20, and a secondouter schematic layer contacting and chemically reacting with firstschematic layer 18 to produce the pigmented adhesive layer 16. It is tobe understood that depiction of first and second schematic layers 18, 20in FIG. 3 is solely for purposes of depicting, in schematic form,aspects of the process of the invention for fabricating the agglomeratedretroreflective glass media 10. Upon microscopic inspection, one wouldsee a pigmented adhesive layer 16 much like that depicted schematicallyin FIG. 2; it would not be expected that one would see discrete separatelayers, such as illustrated 18, 20 in FIG. 3, upon microscopicinspection of an agglomerated retroreflective glass media 10 accordingto the invention.

Average diameter of the relatively larger generally spherical centralglass member designated 12 in the drawings is preferably about 1.2millimeters. A preferable, acceptable range for that diameter is 0.85millimeters to 1.4 millimeters. The extremity of the range for thediameter of the relatively larger generally spherical central glassmember designated 12 in the drawings is preferably from about 0.6 toabout 2.0 millimeters.

The preferable average diameter for the smaller generally sphericalglass members designated 14 in the drawings is 40 micrometers. Thepreferable range of diameter for the smaller generally spherical glassmembers designated 14 in the drawings is from about 30 micrometers toabout 60 micrometers. Preferably, diameter of the smaller generallyspherical glass members designated 14 in the drawings can range low asabout 20 to as high as about 100 micrometers without adversely affectingpractice of the invention.

The pigmented adhesive layer designated 16 in the drawings, which it isto be emphasized represents all of the reagents applied to therelatively larger generally spherical central glass member, preferablyaverages about 15 micrometers in thickness. A preferred range ofthickness for the pigmented adhesive layer designated 16 in the drawingsis from about 10 micrometers to about 40 micrometers. The pigmentedadhesive layer designated 16 in the drawings could preferably range inthickness from as low as about 10 to as high as about 100 micrometers inthickness without adversely affecting performance of the invention.Thickness of pigmented adhesive layer 16 is preferably between about 30%and about 50% of the diameter of smaller generally spherical glassmembers 14.

In one preferred practice of fabricating retroreflective glass mediaaccording to the invention, where the glass media 10 consists of largercentral globular glass members 12, each having a plurality of smallerglobular glass members 14 connected to the central member 12, and themedia are useful for highway marking, the process commences withassembling a supply of largely spherical, essentially clear, relativelylarger globular glass members referred to sometimes herein as “beads”.Suitable amounts of a first silane and water are added and the resultingcombination is mixed for about thirty (30) seconds. Resin and water (toaccelerate) are added and the resulting mixture blended again for aboutthirty (30) seconds. Next, dry pigment is then added, with the pigmentbeing either white if a white color is desired, or a combination ofwhite and yellow pigment if a yellow color is desired, and the resultingcombination blended for about one-hundred twenty (120) seconds. Acrosslinker-blend comprising a cross-linker, a second preferred silane,and a plasticizer, all of which have already been mixed, is then addedand the newly resulting mixture blended for about seventy-five (75)seconds. Next the smaller glass members, that are preferably generallyspherical or at least rounded in form, are added and the resultingmixture blended for about thirty (30) seconds. Finally, an anti-wickingagent is added and the resulting mixture blended for about forty-five(45) seconds. The anti-wicking agent is a temporary coating thatprevents the two-component epoxy or polyurea liquid paint applied to theroad, onto which the beads are applied or dropped, from wicking up thesides of the agglomerated beads and encapsulating the small beads whichwould otherwise prevent the small beads from contributing to theretroreflectivity of the product. This allows for higherretroreflectivity results on the road as more of the smaller beads areexposed. The anti-wicking agent is not permanent and will wear away withage, when in service. An additional advantage of using the anti-wickingagent is that it allows the agglomerate, namely the agglomerated beads,to sink into the coating sufficiently to maintain adhesion to the roadpaint, and does not prevent adhesion between the agglomerated bead outersurface and the road paint.

In this practice of the invention all of the processing, includingmixing of the various reagents, allowing time for the pigment and otherreagents to cover the initial group of larger beads and for the chemicalreactions to occur causing adherence of the small spherical glassmembers to the larger glass beads, occurs completely over a period ofabout five and one-half minutes. All of these steps are performed atambient conditions, typically at room temperature when performedindoors.

In a more specific preferred practice for fabricating retroreflectiveglass media according to the invention, where the retroreflective glassmedia comprise larger central generally spherical glass members witheach having a plurality of smaller generally spherical glass membersconnected to the central member, for providing either white or yellow,according to the pigment(s) selected, reflected light when used forhighway marking, the method includes assembling a supply of generallyspherical essentially clear larger glass members that will amount toabout 1000 parts by weight relative to the other reagents. Between zero(0) and about two (2) parts by weight of a first silane and betweenabout zero (0) and about one (1) part by weight of water are blendedwith the supply of the larger, spherical glass members into a mixture.Next, from about four (4) to about twenty (20) parts by weight of resinand about one-tenth (0.1) to about two-tenths (0.2) parts by weight ofan accelerator (water is the preferred accelerator) are blended into themixture. Subsequently, from about two (2) to about thirty (30) parts byweight of one or more selected pigments are blended into the mixture.Next the crosslinker-blend comprising from about zero (0) to about three(3) parts by weight of plasticizer; from about six (6) to about thirty(30) parts by weight of a crosslinker and from about zero (0) to abouttwo (2) parts by weight of a second silane, all of which have previouslybeen mixed together, are blended into the mixture, whereupon from abouttwo hundred (200) to about four hundred (400) parts by weight of thesmaller glass members are blended into the mixture until the largergenerally spherical glass members are substantially covered by thesmaller members and the smaller members are secured to the largermembers by a layer comprising the first silane and water, the resin andaccelerator, the pigment, the crosslinker-blend. Finally from aboutone-tenth (0.1) to about one-half (0.5) by weight of an anti-wickingagent is blended into the mixture.

In a still more preferred practice of the invention, the first silanemay comprise from about one-half (0.5) to about one (1) part by weight;the water may comprise from about one-tenth (0.1) to about one-half(0.5) part by weight; the resin may comprise from about five (5) toabout twelve (12) parts by weight and the water (as an accelerator) maycomprise from about one-tenth (0.1) to about two-tenths (0.2) parts byweight; the pigment may comprise from about five (5) to about fifteen(15) parts by weight; the crosslinker-blend may be comprised of fromabout two-tenths (0.2) of one part to about two (2) parts by weight of aplasticizer; from about six (6) to about twelve (12) parts by weight ofa crosslinker and from about one-half (0.5) of one part to about onepart by weight of a second silane, all of which have been previouslymixed together the smaller generally spherical glass members maycomprise about two hundred (200) parts by weight; and the anti-wickingagent may comprise from about one-tenth (0.1) to about one-half (0.5)parts by weight, all relative to 1000 parts by weight of large beads.

In an even more preferred version of the inventive method forfabricating agglomerated retroreflective glass media consisting oflarger central essentially spherical glass members, each having aplurality of smaller spherical glass members connected to the centralmember, for providing either white or yellow reflective light, accordingto the color desired, when used for highway marking, the first silane ispreferably about one part by weight relative to 1000 parts by weight oflarge beads; the water is preferably about one-quarter (0.25) of onepart by weight; the resin is preferably about nine (9) parts by weight,the water (as an accelerator) is preferably about one-tenth (0.1) of onepart to about two-tenths (0.2) of one part by weight; the pigment ispreferably about twelve (12) parts by weight; the crosslinker-blend iscomprised of preferably about four-tenths (0.4) of one part by weight ofplasticizer, preferably about ten (10) parts by weight of crosslinkerand preferably about one (1) part by weight of the second silane; allrelative to 1000 parts by weight of large beads, the smaller glassspheres may be in parts by weight relative to 1000 parts by weight oflarge beads and the anti-wicking agent is preferably about four-tenths(0.4) by weight, relative to 1000 parts by weight of large beads.

In an alternate, equally preferred practice for fabricatingretroreflective glass media according to the invention, where the glassmedia comprise larger central generally spherical glass members eachhaving a plurality of smaller generally spherical glass membersconnected to the central member, and the media are useful for highwaymarking, the process commences with assembling a supply of generallyspherical, essentially clear, relatively larger glass members referredto sometimes herein as “beads”, as noted above. Suitable amounts of afirst silane and water are added and the resulting combination is mixedfor thirty (30) seconds.

Resin and water (as an accelerator) are then added, and blended with thecombination for about thirty (30) seconds.

Next, one or more selected dry pigments may be added and the resultingmixture blended for about one hundred twenty (120) seconds.

Next, the crosslinker-blend (comprising plasticizer, crosslinker and asecond preferred silane, all previously mixed together) is then addedand blended for about seventy-five (75) seconds. During thisseventy-five (75) second blending period, at about the thirty (30)second mark, about ten percent (10%) to twenty percent (20%) of thetotality of the smaller glass members used in the process, which arealso preferably generally spherical in form, are sprinkled into mixtureover the course of the remaining forty-five (45) seconds of blendingtime. Next, the remaining portion of the smaller glass members are addeden mass and the resulting mixture is blended for thirty (30) seconds.

Finally, the anti-wicking agent is added and the resulting mixtureblended for about forty-five (45) seconds.

During the manufacture of the agglomerated beads, after the silane,resin, pigment and crosslinker-blend have been added, but before thesmall beads are added, the larger beads, which are coated uniformly withthe mixture, are prone to sticking together, which prevents the entiresurface of each larger bead from being available for placement of thesmaller beads. To prevent this premature adhesion, a small quantity ofthe smaller beads is trickled into the mixture to dust the larger beadsin advance of the bulk addition of the remaining smaller beads. By usingthis “dusting” technique, a full batch results without any “clumping” oflarger beads, and with 100% coverage of the large bead with small beadsover 100% of the large bead surfaces.

As in the above first described preferred practice of the invention, allof the processing, mixing the various reagents, allowing time for themixture to cover the initial group of larger glass members and for thechemical reactions to go to completion, resulting in adherence of thesmall spherical glass members to the larger glass members with ananti-wick coating, occurs over a period of about five and one-halfminutes. All steps are preferably performed in ambient conditions,typically at room temperature.

The invention further embraces a pavement for vehicular travel andstorage thereon, having enhanced visibility, comprising a loadsupporting layer selected from the group comprising concrete, asphaltand aggregates; a curable viscous material applied to an upper surfaceof the load supporting layer; a plurality of retroreflective elementshaving their lower portions embeddedly retained in the material, withtheir upper portions protruding above the surface of the material, witheach retroreflective element having a generally globular glass centralmember, a pigmented adhesive layer over the central member, a pluralityof peripheral smaller globular glass members connected to the centralmember by the pigmented adhesive layer, and an anti-wicking agent.

The invention further includes a method for enhancing visibility ofboundaries, lane lines and the like on pavement comprising applying acurable viscous material to a selected pavement portion, such as aboundary, lane line, and the like, for which visibility is to beenhanced, in a thickness to embeddedly retain lower portions ofgenerally globular retroreflective elements having generally globularglass central members, pigmented adhesive layers over the centralmembers, and a plurality of peripheral globular glass members connectedto the central members by the pigmented adhesive layers, such that upperportions of the globular retroreflective elements protrude above thematerial; applying the globular retroreflective elements to the materialto an extent that the elements embed themselves sufficiently to beretained by the material when the material has cured; and permitting thematerial to cure thereby retaining the embedded globular retroreflectiveelements therein.

Preferred Reagents

The larger single glass beads that form the center of agglomeratedreflective beads in accordance with the invention are preferablyVisibead II Plus beads available from Potters Industries, Inc. in ValleyForge, Pa. These beads range in size from 14 to 20 mesh and have a highpercentage population that are round.

The silane is preferably Silquest 1120 available from GE AdvancedMaterials at 187 Danbury Road, Wilton, Conn. 06897.

The white pigment is preferably Tiona 696 titanium dioxide availablefrom Millennium Chemicals, 20 Wight Avenue, Suite 100, Hunt Valley, Md.21030.

The yellow pigment is preferably Hansa yellow 2GX 70S available fromClariant Corporation, 500 Washington Street, Coventry, R.I. 02416.

The resin for making the resin-pigment intermediate, when theintermediate is used, is preferably Desmophen NH1220, an aspartic esteramine functional resin available from Bayer Materials Science, 100 BayerRoad, Pittsburgh, Pa. 15205.

The preferred accelerator is water.

The plasticizer is preferably Benzoflex 131, available from VelsicolChemical Company, 10400 W. Miggins Road, Suite 600, Rosemont, Ill.60015.The preferred aliphatic polyisocyanate is Desmodur N3300, alsoavailable from Bayer Materials Science. The aliphatic polyisocyanate issometimes referred to herein as a “crosslinker” or as a “resincross-linker”.

The second amino silane is preferably Silquest 1170, also available fromGE Advanced Materials

The smaller glass beads are preferably 1.9 index of refraction glassbeads available from Flex-O-Lite, Inc., 125 Cassens Court, Fenton, Mo.63036.

The preferred anti-wicking agent is Unidyne TG-658 (fluoroalkyl acrylatecoopolymer in solution) from Daiken Industries Ltd, Osaka, Japan.Secondary preferences for anti-wicking agents are Capstone ST-100(formerly Zonyl 8740, fluorochemical dispersion) from DuPont,Wilmington, Del or Silblock SO (silane ester oligomer solution) fromMomentive Performance Materials, Albany, N.Y.

Test and Measurement Procedures

The agglomerated retroreflective glass media fabricated according to theinvention have been tested and measured for their retroreflectivitycharacteristics, for their compliance with applicable colorspecifications, for their pavement coverage characteristics, forresistance to abrasion, and for resistance to wear. The agglomeratedretroreflective glass media in accordance with the invention have beenfound to have characteristics and values, as respecting theseparameters, that are superior in nearly all respects to knowncommercially available reflective glass highway marking materials.

Retroreflectivity of the agglomerated retroreflective glass mediamanifesting aspects of the invention were measured using the method setforth in ASTM Specification E1710 entitled “Test Method for Measurementof Retroreflective Pavement Marking Materials with CEN PrescribedGeometry Using Portable Reflectometer.” In measuring retroreflectivity,the agglomerated retroreflective glass media were tested (i) alone withthe agglomerated retroreflective glass media in a line along a tapewithout any background paint, (ii) with the agglomerated retroreflectiveglass media positioned alone on a tape after handling and packagingsubsequent to manufacturing, (iii) with the agglomerated retroreflectiveglass media alone on tape after a shake test (described below) of theagglomerated retroreflective glass media, (iv) with the agglomeratedretroreflective glass media placed alone on a painted line, and (v) withthe agglomerated retroreflective glass media positioned together withstandard glass beads used for highway marking on a painted line in alaboratory after the media and beads had been tested for wear accordingto the wear test described below.

Results from measuring retroreflectivity are given for the examples andfield trials below where retroreflectivity is expressed in millicandelasper square meter per lux, which is the unit of retroreflectivity asspecified in ASTM E1710. All measurements of retroreflectivity were madeusing a commercially available Mirolux 30 retroreflectometer followingthe procedure set forth in ASTM E1710.

Color of the agglomerated retroreflective glass media in accordance withthe invention was measured following the procedure set forth in ASTME1349 entitled “Test Method for Reflectance Factor and Color bySpectrophotometer Using Bi-Directional Geometry” to determine compliancewith ASTM D6628, entitled “Standard Specification for Color of PavementMarking Materials,” which is the applicable standard. One measurement ofthe color of the agglomerated retroreflective glass media in accordancewith the invention was made with the media freely standing, beingstacked one on another on a base. A second measurement of the color ofthe agglomerated retroreflective glass media in accordance with theinvention was made with the media interspersed with standard highwaymarking glass beads on a painted line. A third measurement of the colorof the agglomerated retroreflective glass media in accordance with theinvention was made after the agglomerated retroreflective glass mediawere interspersed with standard glass highway marking beads on a paintedline after wear testing pursuant to the wear test procedure describedbelow.

For all of agglomerated retroreflective glass media, both white andyellow, fabricated according to the examples herein that are set forthbelow, the color always fell within the ASTM D6628 color box, and alsowithin the more stringent State of Virginia color box for white andyellow agglomerated beads. This was the case under all measurementconditions.

Evaluation of the coverage of the agglomerated retroreflective glassmedia in accordance with the invention was based on viewing theagglomerated retroreflective glass media under a microscope using fromtwenty to forty times magnification. This resulted in subjective viewsas to the coverage and provided empirical data consistent with themeasured values of retroreflectivity. The coverage afforded by theagglomerated retroreflective glass media in accordance with theinvention was observed and empirical data recorded as retroreflectivitywas measured. This was done (i) viewing the agglomerated retroreflectiveglass media alone, immediately after manufacture, (ii) viewing theagglomerated retroreflective glass media alone after being handled andpackaged in the manufacturing facility, and (iii) viewing theagglomerated retroreflective glass media alone after having undergonethe shake test described below.

Agglomerated retroreflective glass media according to the invention havebeen further evaluated using a “shake test” designed to compare batchesof agglomerated retroreflective glass media one to another and tosimulate severe abrasion of the agglomerated retroreflective glassmedia. In the shake test, fifty (50) grams of agglomeratedretroreflective glass media according to the invention are combined in asteel one pint can with one hundred (100) grams of grinding media,namely one-half inch by one-half inch Burundum ceramic media availablefrom Fisher Scientific. The can is then shaken vigorously for 60seconds. After shaking, a 20 mesh screen is used to sieve out any loose,very fine generally spherical glass members. Material that passesthrough the 20 mesh screen, and hence is smaller than 20 mesh, is thenweighed and recorded as a percentage of the agglomerated retroreflectiveglass media fabricated according to the invention.

The inventors also devised a wear test to expose a finished stripe,consisting of paint having agglomerated retroreflective glass mediaaccording to the invention applied thereto and standard highway markingglass beads also applied thereto, to simulate exposure to severecontinuous high speed rubber wheel traffic. A sample stripe is preparedon concrete with epoxy paint. Agglomerated retroreflective glass mediaaccording to the invention and standard highway marking beads areapplied to the epoxy paint stripe. Retroreflectivity is measured andcolor determined for the stripe, using the ASTM procedures and equipmentdescribed above, both before and after the test. For the test, four-inchdiameter rubber wheels, each weighted down with twenty pound weights andspinning at a speed of 176 revolutions per minute, run on a ten-inchdiameter track to which the epoxy paint stripe, the agglomeratedretroreflective glass media, and standard highway marking beads havebeen applied, for sixty (60) minutes, with a short interruption aftereach ten minute segment so that temperature does not rise too high dueto friction.

After the wear test, measured retroreflectivity has ranged from 800 to1,000 for both white and yellow samples of the agglomeratedretroreflective glass media according to the invention. Moreover, boththe white and the yellow samples of the agglomerated retroreflectiveglass media according to the invention remained in the color box,defined by ASTM D6628, as set forth above, after the wear test.

The test results are set forth, as applicable to the agglomeratedretroreflective glass media, with the respective examples.

EXAMPLE 1

Agglomerated yellow retroreflective beads for highway marking inaccordance with the invention were fabricated in a process performedentirely at room temperature by initially combining one quarter gram ofwater, one gram of amino silane and one thousand grams of glass beads.The glass beads were the preferred Visibead II Plus beads available fromPotters Industries, Inc. in Valley Forge, Pa. The beads ranged in sizefrom 14 to 20 mesh and had a high percentage population that were round.The silane was the preferred Silquest 1120 available from GE AdvancedMaterials at 187 Danbury Road, Wilton, Conn. 06897. The silane providedchemical adhesion for the initial set of 14 to 20 mesh glass beads withsubsequent reagents. The water hydrolyzed the silane for added adhesionto the large beads.

A mixture of pigments was prepared consisting of one part yellowpigment, one part white pigment and two parts resin, all such partsbeing by weight, with the mixture weighing seven (7.0) grams. The whitepigment was the preferred Tiona 696 titanium dioxide available fromMillennium Chemicals, 20 Wight Avenue, Suite 100, Hunt Valley, Md.21030; the yellow pigment was the preferred Hansa yellow 2GX 70Savailable from Clariant Corporation, 500 Washington Street, Coventry,R.I. 02416; and the resin was the preferred Desmophen NH1220, anaspartic ester amine functional resin available from Bayer MaterialsScience, 100 Bayer Road, Pittsburgh, Pa. 15205.

Once the pigment-resin mixture was prepared, it was added to the mixtureof the beads, the silane and water, and blended therewith for 30seconds.

A plasticizer, namely the preferred Benzoflex 131, available fromVelsicol Chemical Company, 10400 W. Miggins Road, Suite 600, Rosemont,Ill. 60015, in the amount of thirty-five hundredths of a gram, and 7.88grams of the preferred Desmodur N 3300 aliphatic polyisocyanate, alsoavailable from Bayer Materials Science, were added and the mixture wasthen blended for one minute.

Next one gram of the preferred second amino silane, Silquest 1170, alsoavailable from GE Advanced Materials, was added and the mixture blendedvery briefly whereupon 300 grams of very small glass beads, much smallerthan the initial glass spheres forming the core of the agglomeratedglass bead, were added to the mixture. The small glass beads were thepreferred 1.9 index of refraction glass beads available fromFlex-O-Lite, Inc., 125 Cassens Court, Fenton, Mo. 63036. The resultingmixture was then blended for one and one-half minutes. A quarter gram ofwater was also added and blending continued for an additional thirtyseconds. The resulting agglomerated retroreflective beads were brightyellow. Total time for the procedure was five (5) minutes.

The resulting mixture was passed over a twenty mesh screen. Only anegligible, essentially immeasurable, amount of material passed thoughtthe twenty mesh screen.

Upon conclusion of the process retroreflectivity was measured as 1100.

EXAMPLE 2

Agglomerated white retroreflective beads for highway marking werefabricated in a process performed entirely at room temperature byinitially combining one quarter gram of water, one gram of amino silaneand one thousand grams of glass beads and mixing for about 30 seconds.The glass beads were Visibead II Plus beads, the availability of whichis set forth above. The beads ranged in size from 14 to 20 mesh and hada high percentage population that were round. The silane was Silquest1120, the availability of which is set forth above. The silane providedchemical adhesion for the initial set of glass beads with subsequentreagents and the water hydrolyzed the silane for added adhesion, asexplained above.

A mixture was prepared consisting of one part white pigment and one partresin, such parts being by weight, with the mixture weighing eight (8.0)grams. The white pigment was Tiona 696 titanium dioxide available, theavailability of which is set forth above while the resin was DesmophenNH1220, an aspartic ester amine functional resin, the availability ofwhich is set forth above.

Once the pigment-resin mixture was prepared, it was added to the mixtureof the beads, the silane and water, and blended therewith for aboutthirty seconds.

A plasticizer, namely Benzoflex 131, the availability of which is setforth in previous examples, in the amount of one-half (.50) of a gram,and 8.08 grams of Desmodur N 3300 aliphatic polyisocyanate, theavailability of which is set forth above, were added and the mixture wasthen blended for about one minute.

Next one gram of a second amino silane, this time Silquest 1170, theavailability of which is set forth in previous examples, was added and300 grams of small glass beads, namely smaller than the Visibead II Plusglass beads addressed above, were also added to the mixture. The smallglass beads were 1.9 index of refraction glass beads, the availabilityof which is set forth in previous examples. The resulting mixture wasthen blended for one and one-half minutes. A quarter gram of water wasadded and blending continued for an additional thirty seconds. Theresulting retroreflective beads were brilliant white. Total time for theprocedure was four (4) minutes.

The resulting mixture was passed over a twenty mesh screen. Only anegligible, essentially immeasurable amount of material passed thoughtthe twenty mesh screen to be recycled as small beads.

Upon conclusion of the process retroreflectivity was measured as 960.After undergoing the shake test, 3.17 grams of material passed throughthe twenty mesh screen, indicating that only slightly greater thanthirteen percent (13%) of the small beads had broken the adhesive bondto the larger, central beads. When measured after the shake test,retroreflectivity was 800.

EXAMPLE 3

Agglomerated retroreflective white beads for highway marking werefabricated in a process performed entirely at room temperature byinitially combining one quarter gram of water, one gram of amino silaneand one thousand grams of glass beads and mixing for about 30 seconds.The glass beads were Visibead II Plus beads, available as set forthabove. The beads ranged in size from 14 to 20 mesh and had a highpercentage population that were round. The silane was Silquest 1120,available as set forth above. The silane provided chemical adhesion forthe initial set of glass beads with subsequent reagents and the waterhydrolyzed the silane for added adhesion, as explained above.

A mixture was prepared consisting of one part white pigment and one partresin, both such parts being by weight, with the mixture weighing six(6.0) grams. The white pigment was Tiona 696 titanium dioxide available,available as set forth above, while the resin was Desmophen NH1220, anaspartic ester amine functional resin available as set forth above.

Once the pigment-resin mixture was prepared, it was added to the mixtureof the beads, the silane and water, and blended therewith for 30seconds.

A plasticizer, namely Benzoflex 131, available as set forth above, inthe amount of one-half (0.50) of a gram, and 7.96 grams of Desmodur N3300 aliphatic polyisocyanate, available as set forth above, were addedand the mixture was then blended for about thirty (30) seconds.

Next one gram of a second amino silane, this time Silquest 1170,available as set forth above, was added and 300 grams of small glassbeads, namely smaller than the Visibead II Plus glass beads addressedabove, were also added to the mixture. The small glass beads were 1.9index of refraction glass beads, available as set forth above. Theresulting mixture was then blended for one and one-half minutes. Aquarter gram of water was added and blending continued for an additionalthirty seconds. The retroreflective beads were bright white. Total timefor the process was four (4) minutes.

The resulting mixture was passed over a twenty mesh screen. Only anegligible, essentially immeasurable, amount of material passed thoughtthe twenty mesh screen to be recycled as small beads.

Upon conclusion of the process retroreflectivity was measured as 800.After undergoing the shake test, only 0.15 grams of material passedthrough the twenty mesh screen, indicating that less two tenths of onepercent (<0.2%) of the small beads had broken the adhesive bond to thelarger, central beads. When measured after the shake test,retroreflectivity was 600.

EXAMPLE 4

Agglomerated yellow reflective beads for highway marking were fabricatedin a process performed entirely at room temperature by initiallycombining one quarter gram of water, one gram of amino silane and onethousand grams of glass beads and mixing for about 30 seconds. The glassbeads were Visibead II Plus beads, the availability of which is setforth in previous examples. The beads ranged in size from 14 to 20 meshand had a high percentage population that were round. The silane wasSilquest 1120, the availability of which is set forth in previousexamples. The silane provided chemical adhesion for the initial set ofglass beads with subsequent reagents. The water hydrolyzed the silanefor added adhesion.

A mixture of pigments was prepared consisting of one part yellowpigment, one part white pigment and two parts resin, all such partsbeing by weight, with the mixture weighing eight (8.0) grams. The whitepigment was Tiona 696 titanium dioxide available, the availability ofwhich is set forth in previous examples; the yellow pigment was Hansayellow 2GX 70S, the availability of which is set forth in previousexamples; and the resin was Desmophen NH1220, an aspartic ester aminefunctional resin the availability of which is set forth in previousexamples.

Once the pigment-resin mixture was prepared, it was added to the mixtureof the beads, the silane and water, and blended therewith for 30seconds.

A plasticizer, namely Benzoflex 131, the availability of which is setforth in previous examples, in the amount of forty hundredths (0.40) ofa gram, and 7.10 grams of Desmodur N 3300 aliphatic polyisocyanate, theavailability of which is set forth in previous examples, were added andthe mixture was then blended for about one minute.

Next one gram of a second amino silane, this time Silquest 1170, theavailability of which is set forth in previous examples, was added and300 grams of small glass beads, namely smaller than the Visibead II Plusglass beads addressed above, were also added to the mixture. The smallglass beads were 1.9 index of refraction glass beads, the availabilityof which is set forth in previous examples. The resulting mixture wasthen blended for one and one-half minutes. A quarter gram of water wasadded and blending continued for an additional thirty seconds. Theresulting retroreflective beads were bright yellow. Total processingtime was four (4) minutes.

The resulting mixture was passed over a twenty mesh screen. Everythingthat passed through the twenty mesh screen was collected to be recycledas small beads.

Retroreflectivity was 1150.

EXAMPLE 5

In the following example all “parts” are parts by weight of the finishedagglomerated retroreflective beads.

Agglomerated white retroreflective beads for highway marking werefabricated in a process performed entirely at room temperature byinitially combining 0.5 pounds (0.02 parts) of water, 0.98 pounds (0.04parts) of the preferred amino silane and 1824 pounds (75.15 parts) ofthe preferred glass beads, and mixing for between fifteen (15) andthirty (30) seconds. The glass beads were the preferred Visibead II Plusand the silane was the preferred Silquest 1120, both as described above.The silane provided chemical adhesion for the initial set of glass beadswith subsequent reagents and the water hydrolyzed the silane for addedadhesion. After mixing the glass beads were essentially uniformly coatedwith the amino silane.

Twelve (12) pounds (0.49 parts) of the preferred white pigment and 18.14pounds (0.75 parts) of a 50/50 mixture (by weight) of the preferredwhite pigment and the preferred resin were added to the silane-coatedbeads and the resulting mixture blended for about sixty (60) seconds.The white pigment was the preferred Tiona 696 titanium dioxide and theresin was the preferred Desmophen NH1220, aspartic ester aminefunctional resin, both as described above.

16.56 pounds (0.68 parts) of the preferred Desmodur N 3300 aliphaticpolyisocyanate, as described above, was added together with 0.76 pounds(0.03 parts) of the preferred plasticizer, as described above, and themixture blended for sixty (60) seconds.

1.84 pounds (0.08 parts) of the preferred second amino silane, Silquest1170 as described above, 552 pounds (22.74 parts) of the preferred 1.9refractive index glass beads as described above, and 0.5 pounds (0.02parts) of water were also added to the mixture. The resulting mixturewas then blended for forty-five (45) seconds. After mixing, the 1.9index refractive index glass beads had covered and adhered to the largerVisibead II Plus glass beads, resulting in agglomerated retroreflectivebeads for highway marking. The resulting agglomerated retroreflectivebeads had excellent, brilliant white color. Total mix time for theprocedure was 240 seconds.

The resulting collection of agglomerated retroreflective beads waspassed over a vibrating 6 mesh screen to remove any collections of beadsof excessive size resulting from the large volume and mass of materialthat was processed.

The further resulting collection of agglomerated reflective beads wasthen passed over a 20 mesh screen to reclaim, for recycling, anyunadhered small beads.

When measured at the conclusion of the process retroreflectivity wasmeasured as 1500. After the agglomerated generally sphericalretroreflective media were moved to a packaging area, retroreflectivitywas again measured as 1500 and, after being packaged in a bag, measuredretroreflectivity was still 1500. When measured after undergoing theshake test, retroreflectivity was 1300. Only 2.25 grams of unadheredsmall beads passed through the 20 mesh screen after undergoing the shaketest. Coverage of the test surface with the agglomerated generallyspherical retroreflective media was judged to be excellent, as was thebright white color.

EXAMPLE 6

In the following example all “parts” are parts by weight of the finishedagglomerated retroreflective beads.

Agglomerated white retroreflective beads for highway marking werefabricated in a process performed entirely at room temperature byinitially combining 0.25 pounds (0.02 parts) of water, 0.47 pounds (0.04parts) of amino silane and 912 pounds (75.15 parts) of glass beads, andmixing for between fifteen (15) and thirty (30) seconds. The glass beadswere Visibead II Plus and the silane was Silquest 1120, both asdescribed above. The silane provided chemical adhesion for the initialset of glass beads with subsequent reagents and the water hydrolyzed thesilane for added adhesion. After mixing the glass beads were essentiallyuniformly coated with the amino silane.

Six (6) pounds (0.49 parts) of white pigment were added and the mixtureblended for sixty (60) seconds whereupon 9.07 pounds (0.75 parts) offifty-five parts by weight mixture of white pigment and resin were addedto the silane-coated beads and the resulting mixture blended again aboutsixty (60) seconds. The white pigment was Tiona 696 titanium dioxide andthe resin was Desmophen NH1220, aspartic ester amine functional resin,both as described above.

Seven and two-tenth (7.2) pounds (0.68 parts) of Desmodur N 3300aliphatic polyisocyanate, as described above, was added and the mixturewas blended for sixty (60) seconds.

Thirty-eight hundredths (0.38) pounds (0.03 parts) of plasticizer, asdescribed above, was added and the mixture blended for about fifteen(15) seconds.

Eight tenths (.80) pounds (0.08 parts) of a second amino silane,Silquest 1170 as described above, two hundred seventy-six (276) pounds(22.74 parts) of 1.9 refractive index glass beads as described above,and one quarter (0.25) pound (0.02 parts) of water were also added tothe mixture. The resulting mixture was then blended for forty-five (45)seconds. After mixing, the 1.9 index refractive index glass beads hadcovered and adhered to the larger Visibead II Plus glass beads,resulting in agglomerated retroreflective beads for highway marking.Total mix time for the procedure was 240 seconds. The resultingagglomerated reflective beads had an excellent white color.

The resulting collection of agglomerated retroreflective beads waspassed over a vibrating 6 mesh screen to remove any collection of beadsof excessive size resulting from the large volume and mass of materialthat was processed.

The further resulting collection of agglomerated reflective beads wasthen passed over a 20 mesh screen to reclaim, for recycling, anyunadhered small beads.

When measured at the conclusion of the process retroreflectivity wasmeasured as 1500. After the agglomerated generally sphericalretroreflective media were moved to a packaging area, retroreflectivitywas again measured as 1500 and, after being packaged in a bag, measuredretroreflectivity was still 1500. When measured after undergoing theshake test, retroreflectivity was 1400.

EXAMPLE 7

In the following example all “parts” are parts by weight of the finishedagglomerated retroreflective beads.

Agglomerated white retroreflective beads for highway marking werefabricated in a process performed entirely at room temperature byinitially combining 0.25 pounds (0.02 parts) of water, 0.47 pounds (0.04parts) of amino silane and 912 pounds (75.15 parts) of glass beads, andmixing for between fifteen (15) and thirty (30) seconds. The glass beadswere Visibead II Plus and the silane was Silquest 1120, both asdescribed above. The silane provided chemical adhesion for the initialset of glass beads with subsequent reagents and the water hydrolyzed thesilane for added adhesion. After mixing the glass beads were essentiallyuniformly coated with the amino silane.

Six (6) pounds (0.49 parts) of white pigment were added and blended forabout sixty seconds whereupon 9.07 pounds of a 50/50 mix by weight ofwhite pigment and resin were added to the silane-coated beads and theresulting mixture further blended for about sixty (60) seconds. Thewhite pigment was Tiona 696 titanium dioxide and the resin was DesmophenNH1220, aspartic ester amine functional resin, both as described above.

8.28 pounds (0.68 parts) of Desmodur N 3300 aliphatic polyisocyanate, asdescribed above, was added and the mixture was blended for seventy-five(75) seconds.

0.38 pounds (0.03 parts) of plasticizer, as described above, was addedand the mixture blended for about fifteen (15) seconds.

0.92 pounds (0.08 parts) of a second amino silane, Silquest 1170 asdescribed above, 276 pounds (22.74 parts) of 1.9 refractive index glassbeads as described above, and 0.25 pounds (0.02 parts) were also addedto the mixture. The resulting mixture was then blended for sixty (60)seconds. After mixing, the 1.9 index refractive index glass beads hadcovered and adhered to the larger Visibead II Plus glass beads,resulting in agglomerated retroreflective beads for highway marking Theresulting agglomerated reflective beads had an excellent white color.Total mix time for the procedure was 270 seconds.

The resulting collection of agglomerated retroreflective beads waspassed over a vibrating 6 mesh screen to remove any collections of beadsof excessive size resulting from the large volume and mass of materialthat was processed.

The further resulting collection of agglomerated reflective beads wasthen passed over a 20 mesh screen to reclaim, for recycling, anyunadhered small beads.

When measured at the conclusion of the process retroreflectivity wasmeasured as 1500. After the agglomerated generally sphericalretroreflective media were moved to a packaging area, retroreflectivitywas again measured as 1500 and, after being packaged in a bag, measuredretroreflectivity was still 1400. When measured after undergoing theshake test, retroreflectivity was 1400. Only 2.0 grams of unadheredsmall beads passed through the 20 mesh screen after undergoing the shaketest.

EXAMPLE 8

In the following example all “parts” are parts by weight of the finishedagglomerated retroreflective media.

Agglomerated yellow generally spherical retroreflective media forhighway marking were fabricated in a process performed entirely at roomtemperature by initially preparing a dispersion of resin and pigment,with the dispersion comprising three and three quarter (3¾) pounds (0.21parts) of white pigment, which was the preferred Tiona 696 titaniumdioxide, three and three quarter (3¾) pounds (0.21 parts) of yellowpigment, which was the preferred Hansa yellow 2GX 70S, and seven and onehalf (7½) pounds of resin (0.42 parts), which was the preferredDesmophen NH1220 aspartic ester amine functional resin, with theresulting 14.97 pound dispersion amounting to 0.83 parts of the finishedagglomerated generally spherical retroreflective media.

The process next proceeded by combining thirty-eight hundredths (0.38)pounds (0.02 parts) of water, seventy-four hundredths (0.74) pounds(0.04 parts) of the preferred amino silane and 1326 pounds (73.15 parts)of large glass beads, and mixing for between fifteen (15) and thirty(30) seconds. The large glass beads were the preferred Visibead II Plusand the silane was the preferred Silquest 1120, both as described above.The silane provided chemical adhesion for the initial set of large glassbeads with subsequent reagents and the water hydrolyzed the silane foradded adhesion. After mixing, the large glass beads were essentiallyuniformly coated with the amino silane. Next, 2.25 lb (0.12 parts) ofdry Tiona 696 titanium dioxide white pigment and 2.25 lb (0.12 parts) ofHansa yellow 2GX 70S pigment were added and mixed for 60 seconds.

Next, the dispersion was added and the resulting mixture blended forabout sixty (60) seconds.

13.62 pounds (0.75 parts) of the preferred Desmodur N 3300 aliphaticpolyisocyanate, as described above, was added together with 0.63 pounds(0.03 parts) of the preferred plasticizer, as described above, and themixture blended for seventy-five (75) seconds.

1.5 pounds (0.08 parts) of the preferred second amino silane, Silquest1170 as described above, 450 pounds (24.82 parts) of the preferred 1.9refractive index glass beads as described above, and 0.38 pounds (0.02parts) of water were also added to the mixture. The resulting mixturewas then blended for sixty (60) seconds. After mixing, the 1.9 indexrefractive index glass beads had covered and adhered to the largerVisibead II Plus glass beads, resulting in agglomerated sphericalretroreflective media for highway marking The resulting agglomeratedspherical retroreflective media displayed an excellent yellow color.Total mix time for the procedure was 270 seconds.

The resulting agglomerated retroreflective media were passed over avibrating 6 mesh screen to remove any material collections of excessivesize resulting from the large volume and mass of material that wasprocessed.

The further resulting collection of agglomerated retroreflective mediawas then passed over a 20 mesh screen to reclaim, for recycling, anyunadhered small beads.

When measured at the conclusion of the process retroreflectivity wasmeasured as 1500. After the agglomerated generally sphericalretroreflective media were moved to a packaging area, retroreflectivitywas measured as 1450 and, after being packaged in a bag, measuredretroreflectivity was still 1450. When measured after undergoing theshake test, retroreflectivity was 1050.

EXAMPLE 9

In the following example all “parts” are parts by weight of the finishedagglomerated retroreflective media.

Agglomerated generally spherical retroreflective yellow media forhighway marking were fabricated in a process performed entirely at roomtemperature by initially preparing a dispersion of resin and pigment,with the dispersion comprising five (5) pounds (0.21 parts) of whitepigment, which was the preferred Tiona 696 titanium dioxide, five (5)pounds (0.21 parts) of yellow pigment, which was the preferred Hansayellow 2GX 70S, and ten (10) pounds of resin (0.42 parts), which was thepreferred Desmophen NH1220 aspartic ester amine functional resin, withthe resulting 19.96 pound dispersion amounting to 0.83 parts of thefinished agglomerated generally spherical retroreflective media.

The process next proceeded by combining over half (0.5) pounds (0.02parts) of water, ninety-eight hundredths (0.98) pounds (0.04 parts) ofthe preferred amino silane and 1768 pounds (73.15 parts) of large glassbeads, and mixing for between fifteen (15) and thirty (30) seconds. Thelarge glass beads were the preferred Visibead II Plus and the silane wasthe preferred Silquest 1120, both as described above. The silaneprovided chemical adhesion for the initial set of large glass beads withsubsequent reagents and the water hydrolyzed the silane for addedadhesion, as described above. After mixing, the large glass beads wereessentially uniformly coated with the amino silane.

Next, 3.0 lb (0.12 parts) of dry Tiona 696 titanium dioxide whitepigment and 3.0 lb (0.12 parts) of Hansa yellow 2GX 70S pigment wereadded and mixed for 60 seconds.

Next, the dispersion was added and the resulting mixture blended forabout sixty (60) seconds.

18.16 pounds (0.75 parts) of the preferred Desmodur N 3300 aliphaticpolyisocyanate, as described above, was added together with 0.84 pounds(0.03 parts) of the preferred plasticizer, as described above, and themixture blended for seventy-five (75) seconds.

2.0 pounds (0.08 parts) of the preferred second amino silane, Silquest1170 as described above, 600 pounds (24.82 parts) of the preferred 1.9refractive index glass beads as described above, and 0.5 pounds (0.02parts) of water were also added to the mixture. The resulting mixturewas then blended for sixty (60) seconds. After mixing, the 1.9 indexrefractive index glass beads had covered and adhered to the largerVisibead II Plus glass beads, resulting in agglomerated sphericalretroreflective media for highway marking The resulting agglomeratedspherical retroreflective media displayed an excellent yellow color.Total mix time for the procedure was 270 seconds.

The resulting agglomerated retroreflective media were passed over avibrating 6 mesh screen to remove any material collections of excessivesize resulting from the large volume and mass of material that wasprocessed.

The further resulting collection of agglomerated retroreflective mediawas then passed over a 20 mesh screen to reclaim, for recycling, anyunadhered small beads.

When measured at the conclusion of the process retroreflectivity wasmeasured as 1500. After the agglomerated generally sphericalretroreflective media were moved to a packaging area, retroreflectivitywas again measured as 1500 and, after being packaged in a bag, measuredretroreflectivity was 1400. When measured after undergoing the shaketest, retroreflectivity was 1050. Only 4.2 grams of unadhered smallbeads passed through the 20 mesh screen after undergoing the shake test.

Field Trials

Field trials have proven the superiority of the agglomerated generallyspherical retroreflective media of the invention for highway marking.

An initial field trial was performed in the set-up yard of a roadstriping contractor in Parsippany, N.J. A stripe was applied to the yardasphalt at eight miles per hour. The stripe material was Epoplex LS 70yellow liquid road striping material, available from the EpoplexDivision of StonCor Group, Inc. in Maple Shade, N.J. A mixture of six(6) pounds of yellow agglomerated retroreflective glass media,fabricated according to Example 9 above, and ten (10) pounds of standardglass beads for road marking, was applied to the top of the stripe bygravity feed. The feed vehicle moved at eight (8) miles per hour. Therate of application of the yellow agglomerated reflective glass mediaand of the standard glass beads was six (6) pounds of agglomeratedreflective glass media per gallon of Epoplex LS70 liquid material andten (10) pounds of standard glass beads per gallon of Epoplex LS70liquid material. The resulting line was intense yellow, extremelybright, and retained those characteristics at night. Retroreflectivityvaried from 800 to 1000.

A second field trial was conducted in Parsippany, N.J., on East HalseyRoad, which is an approximately one-half mile long road consisting of abase of old asphalt with three or more existing lines on the asphalt.The existing lines were rough with some flaking having occurred. Astripe was applied to the asphalt at eight miles per hour using EpoplexLS 70 yellow liquid road striping material, available from the EpoplexDivision of StonCor Group, Inc. as described above. A mixture of sixpounds of yellow agglomerated retroreflective glass media, fabricatedaccording to Example 9 above, and ten pounds of standard glass beads forroad marking, was applied to the stripe by gravity feed at the same rateas described above, with the vehicle moving at the same speed asdescribed above. Cure of the material was complete in less than five (5)minutes. The resulting line was very yellow, was extremely bright, andretained those characteristics at night. Retroreflectivity rangedbetween 600 and 800 at the beginning of the stripe and between 700 and800 along the central portion of the stripe, in both directions.

In yet another field trial, conducted in Mountain Lakes, N.J, on FannyRoad, where the road base was newly applied one week old asphalt, thesame materials as used in the Parsippany test, applied at the same rateand same speed, were used. After five (5) minutes, cure of the stripingmaterial was so complete that when a car drove across the stripe, nomarks resulted. The lines were bright yellow and retained thatcharacteristic at night. Retroreflectivity was between 800 and 1000 inboth directions.

The inventive chemistry for fabricating the agglomerated reflectivebeads, as set forth in the preceding examples, is advantageous for anumber of reasons. The coupling agents, namely the silanes, reactquickly with the glass and react at reasonable speed with the adhesive.The reactants all have low viscosity at room temperature and hence areeasy to handle. Moreover, the reactants are compatible with pigments,both dry pigments and pigments in dispersion form.

The process aspect of the invention may be practiced in several ways.Specifically, the process of the invention may use dry pigment only, oruse pigment in a dispersion with resin only, or use both dry pigment andpigment dispersed in a resin, to supply the pigment component.

The reactions are all performed at ambient temperatures. No heating orcooling is involved.

The reactions, when complete, are color stable and weather resistant.The agglomerated retroreflective beads do not yellow, loose their glossor degrade as a result of exposure to the ultraviolet spectrum ofsunlight or from outdoor weathering. The reactions have excellent timeprofile characteristics, with gelling commencing in approximately oneminute and hardening very soon thereafter, allowing enough time for theagents to blend and then harden, thereby retaining the small sphericalessentially clear glass beads in fixed connection with the largercentral bead thereby forming the agglomerated retroreflective beadproduct.

Immediately after completion of the manufacturing process, which onlytakes from four to six minutes, the resulting agglomeratedretroreflective beads can be handled in bulk, may be transported, may bepackaged and the like. There is no waiting period required.

The reactions can be accelerated with small catalytic amounts of waterand do not produce gas that could cause foaming and result in opaquenessof the finished agglomerated retroreflective bead product. The chemistryproduces an agglomerated retroreflective bead having excellent physicalproperties including high tensile strength, toughness and high adhesivestrength for adherence of the small spherical glass elements to thelarger central globular glass members. Tensile strength of the adhesivehas been tested to be over 4,500 psi with an elongation of up to 30% anda tensile modulus of 80 kpsi, providing very, very high strength bondingof the smaller glass beads to the central larger bead.

A major advantage of the agglomerated generally sphericalretroreflective media according to the invention is that when whitepigment is used and the media are applied to a striping line, the medialook white in the daytime and at night. Similarly, when the media areprepared with yellow pigment and applied to a yellow line, the yellowmedia looks yellow by day and at night as well. This cannot be said ofmany, if not most, known retroreflective glass based materials.

One practice of the process of applying the agglomerated retroreflectivemedia for highway marking in accordance with the invention is to applythe retroreflective media using a double drop system, where either anepoxy or polyurea two-component material is mixed and applied at athickness of approximately twenty mils whereupon the agglomeratedretroreflective beads are applied at a rate of about five pounds ofbeads per gallon of the mixed, to-component, either epoxy or polyurea,material and then a standard bead, such as an AASHTO M-247 type 1 bead,is applied at the rate of ten or fifteen pounds per gallon of the mixedtwo-component epoxy or polyurea material. A preferred epoxy material foruse with the agglomerated retroreflective media of the invention isEpoplex LS70, available from the Epoplex Division of StonCor Group, Inc.in Maple Shade, N.J. A preferred polyurea material for use with theagglomerated retroreflective media for highway marking is Epoplex LS90,also available from the Epoplex Division of StonCor Group, Inc. in MapleShade, N.J.

One suitable apparatus for performing the mixing and blending functionsin the fabrication of the retroreflective media according to theinvention is the Whiskey Rock two and one-half cubic foot electricmixer, the details of which are available atwhiskey-rock.com/products/CP2528. This mixer is suitable for use inmanufacturing small size batches of the agglomerated retroreflectivemedia according to the invention.

An even more preferable mixer that has the capacity to manufacturelarger size and production batches of the retroreflective agglomeratedglass media according to the invention is the Forberg mixer, the detailsof which are available at www.forbergmixer.com. The Forberg mixer wasused in connection with the procedure set forth in examples five throughnine hereof

Tables describing actual production runs and results are shown below:

TABLE 1 Batch # 1 2 3 4 5 6 Color Yellow Yellow Yellow Yellow YellowYellow Total Weight (in pounds) 2051.9 2051.9 2051.9 2051.9 2051.92051.9 Reagents Weight in pounds (unless otherwise indicated) LargeBeads 1620 1620 1620 1620 1620 1620 Silane 1.25 1.25 1.25 1.25 1.25 1.25Resin 13.0 13.0 13.0 13.0 13.0 13.0 Water (in grams) 60 55 50 55 55 55Titanium Dioxide Pigment 9 9 9 9 9 9 Yellow Pigment 5 5 5 5 5 5Crosslinker Blend 17.0 17.0 17.0 17.0 17.0 17.0 Small Beads for“dustings” 66 66 66 66 66 66 Small Beads 320 320 320 320 320 320Anti-Wicking 0.6 0.6 0.6 0.6 0.6 0.6 Blending process Elapsed times inminutes/seconds START - Large Beads and Silane 0 0 0 0 0 0 Resin 30 3030 30 30 30 All Pigments 1:00 1:00 1:00 1:00 1:00 1:00 Crosslinker Blend3:00 3:00 3:00 3:00 3:00 3:00 Small Beads “dusting” 3:30 3:30 3:30 3:303:30 3:30 Small Beads 4:15 4:15 4:15 4:15 4:15 4:15 Anti-Wicking 4:454:45 4:45 4:45 4:45 4:45 STOP 5:30 5:30 5:30 5:30 5:30 5:30 Product fromMixer/Retroreflectivity* 1192 1120 1105 1006 1084 1186 Product inBag/Retroreflectivty* 1019 991 878 903 945 1019 Retroreflectivity inapplied strip* 987 986 892 872 954 1012 Yield % 98.2 98.3 97.8 97.5 98.797.6 *Retroreflectivity is measured by mcd/sq m/lux (millicandelas persquare meter per lux).

TABLE 2 Batch # 1 2 3 4 5 6 7 8 9 10 Color White White White White WhiteWhite White White White White Total Weight 2058.6 2058.6 2058.6 2058.62058.6 2058.6 2058.6 2058.6 2058.6 2058.6 Reagents Weight in pounds(unless otherwise indicated) Large Beads 1608 1608 1608 1608 1608 16081608 1608 1608 1608 Silane 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 Resin14.6 14.6 14.6 14.6 14.6 14.6 14.6 14.6 14.6 14.6 Water (in grams) 45 5050 50 45 50 50 50 47 45 Titanium Dioxide 18.8 18.8 18.8 18.8 18.8 18.818.8 18.8 18.8 18.8 Pigment Crosslinker Blend 19.2 19.2 19.2 19.2 19.219.2 19.2 19.2 19.2 19.2 Small Beads for 66 66 66 66 66 66 66 66 66 66“dusting” Small Beads 330 330 330 330 330 330 330 330 330 330Anti-Wicking 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Blending ProcessElapsed times in minutes/seconds START - Large Beads 0 0 0 0 0 0 0 0 0 0and Silane Resin 30 30 30 30 30 30 30 30 30 30 All Pigments 1:00 1:001:00 1:00 1:00 1:00 1:00 1:00 1:00 1:00 Crosslinker Blend 3:00 3:00 3:003:00 3:00 3:00 3:00 3:00 3:00 3:00 Small Beads for 3:30 3:30 3:30 3:303:30 3:30 3:30 3:30 3:30 3:30 “dustings” Small Beads 4:15 4:15 4:15 4:154:15 4:15 4:15 4:15 4:15 4:15 Anti-Wicking 4:45 4:45 4:45 4:45 4:45 4:454:45 4:45 4:45 4:45 STOP 5:30 5:30 5:30 5:30 5:30 5:30 5:30 5:30 5:305:30 Product from 978 1178 1152 1128 1112 1215 1158 1264 1205 1164Mixer/Retroreflectivity* Product in 853 1048 1039 1030 980 1101 10251100 1071 1030 Bag/Retroreflectivty* Retroreflectivity in 839 1073 1030964 869 1062 993 1041 887 1020 applied strip* Yield % 99.0 99.3 99.198.9 98.9 98.8 97.9 98.3 98.2 98.9 *Retroreflectivity is measured bymcd/sq m/lux (millicandelas per square meter per lux).

1) A retroreflective device securable to a highway by bonding with aviscous strip applied to the highway prior to solidifying cure of thestrip, comprising: a. a generally globular glass central member; b. apigmented adhesive layer over the central member; c. a plurality ofperipheral globular glass members connected to the central member by thepigmented adhesive layer. 2) The device of claim 1 in which the centralmember is in the range of from about 14 to about 20 mesh and theperipheral members are in the range of from about 325 to about 400 mesh.3) The device of claim 1 wherein the central member is of generallyspherical configuration. 4) The device of claim 1 wherein the peripheralmembers are of generally spherical configuration. 5) The device of claim3 wherein the peripheral members are of generally sphericalconfiguration. 6) The device of claim 1 wherein the pigmented layer is amixture of pigment and resin. 7) The device of claim 6 wherein thepigmented layer is about 40% pigment by weight. 8) The device of claim 1in which the thickness of the pigmented layer is less than the diameterof the peripheral globular glass members. 9) The retroreflective devicefor highway marking of claim 1 wherein the globular central member hasan average diameter of from about six tenths (0.6) of a millimeter toabout two (2.0) millimeters; wherein the pigmented adhesive layer has athickness of from about ten (10) to about fifty (50) micrometers, andthe peripheral globular glass members have an average diameter of fromabout twenty (20) to about one hundred (100) micrometers. 10) The deviceof claim 1 wherein average thickness of the pigmented adhesive layer isfrom about thirty percent (30%) to about fifty percent (50%) of theaverage diameter of the peripheral globular glass members. 11) Thedevice of claim 1 wherein the globular glass central member has anaverage diameter of from about eighty-five hundredths (0.85) of amillimeter to about one and four-tenths (1.4) millimeters; the pigmentedadhesive layer has a thickness of from about ten (10) to about forty(40) micrometers; and the peripheral globular glass members have anaverage diameter of from about thirty (30) to about sixty (60)micrometers. 12) The device of claim 1 wherein the globular glasscentral member has an average diameter of about one and two-tenths (1.2)millimeters; the pigmented adhesive layer has a thickness of aboutfifteen (15) micrometers; and the peripheral globular glass members havean average diameter of about forty-five (45) micrometers. 13) A methodfor fabricating agglomerated retroreflective glass media consisting oflarger central globular glass members, each having a plurality ofsmaller globular glass members connected to the central member, forhighway marking, comprising: a. assembling a supply of largely sphericalessentially clear larger globular glass members; b. adding silane andwater to the supply of larger members; c. blending the silane, water andlarger members into a mixture; d. blending resin and accelerator intothe mixture; e. blending pigment into the mixture; f. blending acrosslinker-blend into the mixture; g. blending the smaller glassmembers into the mixture until the larger globular glass members aresubstantially covered by the smaller members and the smaller members aresecured to the larger members by a layer comprising the first silane,the resin and accelerator, the pigment, the crosslinker-blend; and h.blending an anti-wicking agent into the mixture. 14) The method of claim13 wherein the larger globular glass member have an average diameter offrom about six tenths (0.6) of a millimeter to about two (2.0)millimeters; wherein the layer has a thickness of from about ten (10) toabout fifty (50) micrometers, and the smaller glass members have anaverage diameter of from about twenty (20) to about one hundred (100)micrometers. 15) The method of claim 13 wherein average thickness of thelayer is from about fifteen percent (15%) to about fifty percent (50%)of the average diameter of the smaller glass members. 16) The method ofclaim 13 wherein the larger globular glass members have an averagediameter of from about eighty-five hundredths (0.85) of a millimeter toabout one and four-tenths (1.4) millimeters; the layer has a thicknessof from about ten (10) to about forty (40) micrometers; and the smallerglass members have an average diameter of from about sixty (60) to aboutninety (90) micrometers. 17) The method of claim 13 wherein the largerglobular glass members have an average diameter of about one andtwo-tenths (1.2) millimeters; the layer has a thickness of about fifteen(15) micrometers; and the smaller glass members have an average diameterof about seventy-five (75) micrometers. 18) The method of claim 13wherein the accelerator is water. 19) The method of claim 13 performedwithout temperature control. 20) The method of claim 13 performedwithout the addition of heat. 21) A method for fabricating agglomeratedretroreflective glass media for highway marking, comprising: a.assembling a first supply of generally spherical essentially clear glassbeads where the beads range in size between about 14 and about 20 meshand at least about 80% of the beads are round; b. adding silane andwater to the first beads and blending the silane, water and beads into amixture; c. blending resin and accelerator into the mixture; d. blendingpigment into the mixture; e. blending a crosslinker-blend into themixture; f. blending the smaller glass beads into the mixture forsufficient time to adhere to the generally spherical glass beads; g.blending an anti-wicking agent; h. straining the resulting mixture toremove from the mixture agglomerated glass beads of size excessive forroad marking; and i. straining the remaining mixture to remove loosesmaller glass beads which did not attach to a large glass bead. 22) Amethod for fabricating agglomerated retroreflective glass mediaconsisting of larger central generally spherical glass members, eachhaving a plurality of smaller generally spherical glass membersconnected to the central member, for providing reflected light of apreselected color when used for highway marking, comprising: a.assembling a supply of largely spherical essentially clear larger glassmembers that will amount to about 1000 parts by weight; b. blendingbetween about zero (0) and about two (2.0) parts by weight, relative tothe largely spherical essentially clear glass members, of a first silaneand between zero (0) and about one (1.0) part by weight, relative to thelargely spherical essentially clear glass members, of water togetherwith the supply of larger members into a mixture; c. blending from aboutfour (4.0) to about twenty (20.0) parts by weight, relative to thelargely spherical essentially clear glass members, of resin and fromabout one-tenth ( 1/10) of one part to about two-tenths ( 2/10) of onepart of an accelerator into the mixture; d. blending from about two(2.0) to about thirty (30.0) parts by weight of pigment, relative to thelargely spherical essentially clear glass members, which pigment ischosen to produce the preselected color of reflected light, into themixture; e. blending between about six (6) and about thirty-five (35)parts by weight, relative to the largely spherical essentially clearglass members, of a crosslinker-blend into the mixture; f. blending fromabout two hundred (200) to about four hundred (400) parts by weight,relative to the largely spherical essentially clear glass members, ofthe smaller glass members into the mixture until the larger glassmembers are substantially covered by the smaller members and the smallermembers are secured to the larger members by a layer comprising thefirst silane, the resin and accelerator, the pigment, and thecrosslinker-blend; and g. blending from about one-tenth (0.1) of onepart to about one-half (0.5) of one part of an anti-wicking agent. 23)The method of claim 22 wherein the first silane comprises from about onehalf (0.5) to about one (1.0) part by weight relative to the largelyspherical essentially clear glass members. 24) The method of claim 23wherein the first silane comprises about one (1.0) part by weightrelative to the largely spherical essentially clear glass members. 25)The method of claim 21 wherein the addition of water comprises fromabout one tenth (0.1) to about one half (0.5) part by weight relative tothe largely spherical essentially clear glass members. 26) The method ofclaim 25 wherein the addition of water comprises about one-quarter ofone part (0.25) by weight relative to the largely spherical essentiallyclear glass members. 27) The method of claim 22 wherein the pigmentcomprises from about five (5.0) to about fifteen (15.0) parts by weightrelative to the largely spherical essentially clear glass members. 28)The method of claim 29 wherein the pigment comprises about twelve parts(12.0) by weight relative to the largely spherical essentially clearglass members. 29) The method of claim 22 wherein the resin comprisesfrom about five (5.0) to about twelve (12.0) parts by weight relative tothe largely spherical essentially clear glass members. 30) The method ofclaim 29 wherein the resin comprises about nine parts (9.0) by weightrelative to the largely spherical essentially clear glass members. 31)The method of claim 22 wherein the accelerator is water. 32) The methodof claim 22 wherein the plasticizer comprises from about two-tenths ofone part (0.2) to about two (2.0) parts by weight relative to thelargely spherical essentially clear glass members. 33) The method ofclaim 32 wherein the plasticizer comprises about four tenths of one part(0.4) by weight relative to the largely spherical essentially clearglass members. 34) The method of claim 22 wherein the cross-linkercomprises from about six (6.0) to about twelve (12.0) parts by weightrelative to the largely spherical essentially clear glass members. 35)The method of claim 34 wherein the cross-linker comprises about tenparts (10.0) by weight relative to the largely spherical essentiallyclear glass members. 36) The method of claim 22 wherein the secondsilane comprises from about one half of one part (0.5) to about one(1.0) part by weight relative to the largely spherical essentially clearglass members. 37) The method of claim 36 wherein the second silanecomprises about one part (1.0) by weight relative to the largelyspherical essentially clear glass members. 38) The method of claim 22wherein the smaller glass members comprise about three hundred (300.0)parts by weight relative to the largely spherical essentially clearglass members. 39) The method of claim 22 wherein the pigment is white.40) The method of claim 22 wherein the pigment is a fifty-fifty blend byweight of white and yellow pigment. 41) The method of claim 13 in whichthe adding and blending steps are performed in fewer than six minutes.42) The method of claim 13 in which the adding and blending steps areperformed in fewer than about five minutes. 43) The method of claim 21in which the adding and blending steps are performed in fewer than sixminutes. 44) The method of claim 21 in which the adding and blendingsteps are performed in fewer than about five minutes. 45) The method ofclaim 22 in which the adding and blending steps are performed in fewerthan six minutes. 46) The method of claim 22 in which the adding andblending steps are performed in fewer than about five minutes. 47) Themethod of claim 13 wherein from about ten percent (10%) to about twentypercent (20%) of the smaller glass beads are trickled into the mixtureslowly in advance of the remainder of the smaller glass beads. 48) Themethod of claim 21 wherein from about ten percent (10%) to about twentypercent (20%) of the smaller glass beads are trickled into the mixtureslowly in advance of the remainder of the smaller glass beads. 49) Themethod of claim 22 wherein from about ten percent (10%) to about twentypercent (20%) of the smaller glass beads are trickled into the mixtureslowly in advance of the remainder of the smaller glass beads.